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WO2010117012A1 - Dispositif d'évaluation de la perméabilité et procédé d'évaluation - Google Patents

Dispositif d'évaluation de la perméabilité et procédé d'évaluation Download PDF

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Publication number
WO2010117012A1
WO2010117012A1 PCT/JP2010/056295 JP2010056295W WO2010117012A1 WO 2010117012 A1 WO2010117012 A1 WO 2010117012A1 JP 2010056295 W JP2010056295 W JP 2010056295W WO 2010117012 A1 WO2010117012 A1 WO 2010117012A1
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Prior art keywords
tank
component
film
adsorption
evaluated
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PCT/JP2010/056295
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English (en)
Japanese (ja)
Inventor
敏宏 島田
敏之 管野
基▲みん▼ 南
Original Assignee
Shimada Toshihiro
Kanno Toshiyuki
Nam Kimin
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Application filed by Shimada Toshihiro, Kanno Toshiyuki, Nam Kimin filed Critical Shimada Toshihiro
Priority to JP2010545304A priority Critical patent/JP4759096B2/ja
Publication of WO2010117012A1 publication Critical patent/WO2010117012A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N15/082—Investigating permeability by forcing a fluid through a sample
    • G01N15/0826—Investigating permeability by forcing a fluid through a sample and measuring fluid flow rate, i.e. permeation rate or pressure change
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N15/088—Investigating volume, surface area, size or distribution of pores; Porosimetry
    • G01N15/0893—Investigating volume, surface area, size or distribution of pores; Porosimetry by measuring weight or volume of sorbed fluid, e.g. B.E.T. method
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N2015/086—Investigating permeability, pore-volume, or surface area of porous materials of films, membranes or pellicules

Definitions

  • the present invention relates to a permeability evaluation apparatus and an evaluation method for evaluating the permeation of gas or liquid in a film or thin film.
  • Plastic films have the advantages of being lighter and more impact resistant than glass substrates, having high flexibility and being able to reduce costs. For this reason, in addition to being widely used for PET bottles and food packaging, in recent years, research and development of film-forming technology using plastic substrates has been promoted in the field of image display devices where glass substrates have been used. It has been.
  • the measurement sensitivity with respect to the water vapor permeability of plastic films by the current measuring means is about 1 ppm, and the water vapor permeability required for maintaining the performance of the display device and the like. The value is greatly exceeded. For this reason, due to practical requirements, there is an urgent need to improve measurement sensitivity for oxygen permeability and water vapor permeability of plastic films. Therefore, in order to improve the measurement sensitivity for these permeability, an evaluation method using a mass analyzer as disclosed in Patent Document 1 and Patent Document 2 has been proposed.
  • the film to be measured is installed on the sample stage provided at the boundary between the component introduction tank and the vacuum tank, and the component to be evaluated such as water vapor is introduced into the component introduction tank.
  • JP 2002-357533 A Japanese Patent Laid-Open No. 2005-233943
  • the amount of water vapor released is 1 ⁇ 10 ⁇ 7 Pa ⁇ m 3 / s. Therefore, the real-time measurement of the water vapor permeability of the film, release gas from the inner wall of the apparatus becomes 10 4 times the amount of permeated water, it is difficult to distinguish water release amount from the water permeate flow device inner wall.
  • a barrier film for a film device such as an organic EL display is required to have a water vapor permeability of about 10 ⁇ 6 g / m 2 / day.
  • the measurement sensitivity in the prior art is on the order of 10 ⁇ 4 g / m 2 / day, and the measurement sensitivity is absolutely insufficient.
  • the manufacturing process of the plastic film used for the display device there is a serious practical problem that accurate quality control cannot be performed in terms of oxygen permeability and water vapor permeability.
  • the conventional method also has a problem of long measurement time.
  • the present invention solves the above-mentioned problems, can detect a very small amount of transmission component from a film below the measurement limit according to the prior art with high sensitivity, and can perform analysis accurately and accurately.
  • An object is to provide an apparatus and a permeability treatment method.
  • the present invention is a permeability evaluation apparatus for performing an evaluation on the permeation component of the measured membrane (10),
  • the apparatus adsorbs an evaluation target component by cooling at least a chamber (15) having a permeation component introduction tank (11) and a permeation component passage tank (12), and removes the evaluation target component by stopping cooling or heating.
  • a support jig (14) of the film (10) is disposed on the contact surfaces facing each other, and the support jig ( 14), when the membrane (10) is supported, between the one surface of the membrane (10) and the inner wall of the tank (11) and the other surface of the film (10) and the tank (12).
  • Each has a structure in which a sealed space is formed between the inner wall and
  • the tank (11) is provided with an introduction port (60) and an exhaust port (62) for components to be evaluated,
  • the tank (12) has a structure capable of supplying the component to be evaluated that has passed through the measured membrane (10) to the adsorption / desorption base material (30) through a pipe having a valve.
  • the adsorption / desorption substrate (30) adsorbs the evaluation target component by being cooled, and desorbs the evaluation target component by being cooled or heated.
  • the analysis means (72) provides a permeability evaluation apparatus characterized by having a function of detecting an evaluation target component detached from the base material (30).
  • the analysis means (72) is any one of a mass spectrometer, a gas chromatography, and a vacuum gauge; the chamber (15) further includes a temperature / humidity adjustment means (70), Enabling adjustment of the temperature and humidity of the sealed space of the permeation component introduction tank (11) disposed in the chamber (15); and the permeation component passage tank (12) and the adsorption / desorption substrate.
  • the tank (12) is provided with a permeation component storage tank (13), the tank (12) and the tank (13) are connected via a pipe having a valve, and the tank (13)
  • the structure to be able to supply the component to be evaluated that has passed through the membrane to be measured (10) to the adsorption / desorption substrate (30) through the pipe;
  • the support jig (14) is made of metal Gasket or elastomer gasket Comprising a moisture remover (91) for removing moisture in the inert gas;
  • the adsorption / desorption substrate (30) is provided in a permeation component capture tank (51). It is preferable that
  • the present invention also relates to a permeability evaluation method for evaluating a permeation component of a membrane to be measured, which includes a sampling step for collecting the evaluation target component that has permeated through the membrane to be measured, and a suction evaluation of the sampled evaluation target component. Having an adsorption fixing step of adsorbing and fixing to a release substrate, and an analysis step of analyzing the evaluation target component, In the sampling step, two sealed spaces are formed at positions facing each other across the film to be measured, and the component to be evaluated is placed in one sealed space so that both sealed spaces have equal pressure.
  • the component to be evaluated is adsorbed by cooling, and the adsorption / desorption substrate from which the component to be evaluated is desorbed is cooled by heating or is heated.
  • the collected evaluation target components are adsorbed and fixed,
  • a permeability evaluation method characterized in that, in the analysis step, the cooling is performed on the adsorption / desorption substrate or the component to be evaluated is desorbed by heating or the analysis is performed.
  • the component to be evaluated is water, oxygen, carbon dioxide, nitrogen, ethylene gas, or a volatile organic compound; any one of a mass spectrometer, a gas chromatography, and a vacuum gauge is used in the analysis step. It is preferable to replace the two sealed spaces with an inert gas of equal pressure in advance before the sampling step.
  • trace amounts of water vapor permeability and oxygen permeability of various membranes can be measured accurately, accurately, and quickly.
  • the figure which calculated the water vapor transmission rate from the pressure change shown in FIG. The figure explaining the relationship between a pressure change and the amount of water vapor transmission.
  • the apparatus of the present invention is a permeability evaluation apparatus that performs an evaluation on the permeability of a very small amount of water vapor, oxygen, or the like on a film to be measured 10 such as a plastic film.
  • the apparatus of the present invention has at least a chamber 15 having a permeation component introduction tank 11 and a permeation component passage tank 12, and an adsorption desorption that adsorbs the evaluation target component by cooling and desorbs the evaluation target component by stopping cooling or heating.
  • the separation substrate 30, an analysis means 72 for analyzing the evaluation target component, and a mechanism 80 for supplying at least the inert gas to the permeation component passage tank 12 are provided.
  • the cooling in the above varies depending on the component to be evaluated, for example, liquid nitrogen (77K), liquid helium (4K), or the like is preferably used as a refrigerant and is performed at an extremely low temperature.
  • a support jig 14 for the film to be measured 10 is disposed on the contact surfaces facing each other.
  • the film to be measured 10 is supported by the support jig 14, between one surface of the film 10 and the inner wall of the tank 11 and between the other surface of the film 10 and the inner wall of the tank 12.
  • Each has a structure in which a sealed space is formed.
  • the component introduction tank 11 includes at least an introduction port 60 and an exhaust port 62 for a component to be evaluated.
  • the introduction port 60 and the exhaust port 62 are preferably connected to pipes (41, 42) each having a valve.
  • the permeation component passage tank 12 has a structure capable of supplying the component to be evaluated that has permeated through the film to be measured 10 to the adsorption / desorption substrate 30 through a pipe having a valve.
  • adsorption / desorption base material 30 As the adsorption / desorption base material 30, a substrate that adsorbs the evaluation target component by being cooled and desorbs the evaluation target component by being cooled or heated.
  • the evaluation target component that has passed through the measurement target film 10 is adsorbed and collected by cooling the adsorption / desorption substrate 30.
  • the valve is closed, and then the adsorption / desorption substrate 30 is stopped or heated to desorb the permeated evaluation target component and analyze the total amount.
  • Means 72 can be provided.
  • analysis means 72 one having a function of detecting the evaluation target component detached from the base material 30 is used.
  • analysis means include a mass spectrometer, gas chromatography, or vacuum gauge.
  • an ultra-high evacuation device 73 is installed as appropriate.
  • the inert gas supply mechanism 80 supplies an inert gas to at least the permeation component passage tank 12.
  • the evaluation target component permeates the membrane 10 due to the difference in partial pressure of the evaluation target component while the tank 11 and the tank 12 are at the same pressure. Since evacuation of the tank 12 is not required, damage to the apparatus and the film 10 can be reduced and the reproducibility of the measurement result can be improved.
  • an inert gas tank 87 filled with an inert gas, and inert gas supply pipes 82 and 84 connecting the tank 87 and the chamber 15, and the tank 87 and the tank 13 are given. Can do. These tubes preferably comprise valves.
  • the mechanism 80 By providing the mechanism 80 with a moisture remover 91 to remove moisture in the inert gas and then supplying it to the apparatus of the present invention, the reproducibility of the measurement can be further improved.
  • the inert gas it is preferable to use a rare gas such as helium, neon, or argon in addition to the nitrogen gas.
  • the pressure of the tanks 11 and 12 at the time of measurement is not particularly limited as long as it is equal, but by setting the atmospheric pressure to be the same as the external pressure, the stress applied to the apparatus can be minimized and labor for exhaust can be saved. Therefore, it is preferable.
  • the chamber 15 preferably further includes a temperature / humidity adjusting means 70.
  • a temperature / humidity adjusting means 70 By adjusting the temperature and humidity in the chamber 15 and adjusting the temperature in the tanks 11 and 12 indirectly, the sensitivity of a very small amount of transmitted components from the film to be measured under the desired temperature and humidity conditions is good. Detection is possible. Further, by making the temperature and humidity in the tanks 11 and 12 and the chamber 15 outside thereof equal, the gradient of temperature and humidity can be eliminated and the measurement can be performed under stable conditions, so that the reproducibility of the measurement results is improved. Can do.
  • FIG. 1 it is also one of the preferable embodiments of the apparatus of the present invention to provide a permeated component storage tank 13 between the permeated component passage tank 12 and the adsorption / desorption substrate 30.
  • the tank 12 and the tank 13 are connected via a pipe having a valve.
  • the forced circulation fan 21 is useful for sending the component to be evaluated that has passed through the membrane 10 from the tank 12 to the tank 13.
  • the permeate concentration in the tank 12 and the tank 13 is kept constant by opening the valve of the pipe and forcibly circulating the gas in the tank 12 and the tank 13 with the circulation fan 21. be able to. Further, when the base material 30 is cooled, the gas contracts and the inside of the apparatus is depressurized. Therefore, if the tank 12 and the base material 30 are connected, the film 10 may be deformed or damaged by repeated measurement. In addition, the processed portion such as a barrier coating film of the film may be damaged.
  • the valve between the tanks 12 and 13 is closed, It is preferable because both sides of the film 10 can be maintained at an equal pressure (for example, atmospheric pressure) and the film 10 can be protected from damage.
  • the forced circulation fan 21 include a heat-bakable fan or a diaphragm pump.
  • the support jig 14 that does not impair the sealing performance even after repeated use over a long period of time.
  • the support jig 14 that can be suitably used in the apparatus of the present invention include a metal gasket and an elastomer gasket.
  • the metal gasket base material for example, copper, stainless steel, aluminum alloy, titanium alloy, silver alloy, or indium alloy can be used.
  • the adsorption / desorption base material 30 in the permeation component capturing tank 51.
  • desorption of the evaluation object component to the base material 30 can be equalize
  • the cooling means for the base material 30 include a structure in which a refrigerant container 52 of liquid nitrogen or the like is installed and a tank 51 containing the base material 30 is immersed in the refrigerant container 52. In this case, a material that has high thermal conductivity and can withstand low temperatures is used as the material for forming the tank 51.
  • the present invention is not limited to the above configuration, and the base material 30 itself can be sufficiently cooled by a refrigerant such as liquid nitrogen.
  • a refrigerant such as liquid nitrogen.
  • the evaluation target component is adsorbed on the base material 30, and the cooling is stopped. Any method may be used as long as the structure to be evaluated is desorbed.
  • the movement of the permeated evaluation target component from the tank 12 or the tank 13 to the base material 30 may be diffusion by opening a valve, but a pipe 32 having a circulation fan is installed in the tank 51. The gas may be circulated at atmospheric pressure using the pipe. In this way, the component to be evaluated from the tank 12 or the tank 13 can be adsorbed to the base material 30 more efficiently.
  • the adsorption / desorption substrate 30 It is preferable to use a material having a large surface area or a material having a high thermal conductivity as the adsorption / desorption substrate 30.
  • the material of the adsorption / desorption substrate 30 that is preferably used in the apparatus of the present invention is determined according to the component to be evaluated and cannot be generally specified. Mention may be made of foam metals such as structures and porous stainless steel.
  • the cooling temperature of the adsorption / desorption base material 30 also depends on the evaluation target component to be adsorbed and cannot be generally stated, but is, for example, a liquid nitrogen temperature ( ⁇ 196 ° C.) or less. Since liquid nitrogen is inexpensive, the measurement can be performed economically. According to the study by the present inventors, when the component to be evaluated is water vapor, the adsorption / desorption substrate is cooled to the liquid nitrogen temperature to adsorb moisture, and then the inside of the permeation component capturing tank 51 is cooled. It was found that even if the gas in the tank was removed by evacuation, the water adsorbed on the base material hardly sublimated and was not lost.
  • sucked to the base material is sublimated rapidly by stopping cooling or heating a base material.
  • the amount of water adsorbed on the base material 30 by liquid nitrogen cooling can be accurately quantified, and accurate evaluation becomes possible.
  • the materials constituting the tanks 11, 12, 13, 51, the chamber 15, the support jig 14, and the pipe having the valve have a gas release rate of 1 ⁇ 10 when the temperature of the base material 30 is raised. It is preferable to use a material having a pressure of ⁇ 9 Pa ⁇ m 3 / m 2 s or less. Examples of such materials include copper, stainless steel, aluminum alloy, titanium alloy and silver alloy.
  • the permeability evaluation method of the present invention can be carried out using the permeability evaluation apparatus of the present invention having the configuration shown in FIG.
  • the method includes a sampling step for sampling at least the evaluation target component that has permeated through the measured film 10, an adsorption fixing step for adsorbing and fixing the collected evaluation target component to the adsorption / desorption base material 30, and the adsorption fixation An analysis step of desorbing the component to be evaluated from the substrate 30 and analyzing it;
  • the sampling step first, the film to be measured 10 is sandwiched between the permeation component introduction tank 11 and the permeation component passage tank 12 to form two sealed spaces that sandwich the film 10.
  • the component to be evaluated is introduced into the sealed space on the permeable component introduction tank 11 side, the inert gas is introduced into the sealed space on the permeable component passage tank 12 side, and both sealed spaces are brought to the same pressure.
  • the evaluation target component permeates the membrane 10 due to the difference in partial pressure between the evaluation target components in the tanks 11 and 12,
  • the transmitted evaluation target component accumulates in the tank 12.
  • the holding time for this permeation varies depending on the permeability of the membrane 10 and the component to be evaluated, and cannot be generally specified, but is, for example, 1 to 20 hours.
  • the holding time for transmission may be about 40 hours, and considering that the measurement sensitivity has not reached the desired level, the present invention is Even holding time alone is epoch-making and its practical value is extremely high.
  • all the valves of the pipes connected to the tanks 11 and 12 may be closed and held, or the valves of the pipes 20 and 22 may be opened to circulate the gas between the tanks 13 and 13. Good.
  • the pressure in the tanks 11 and 12 is not particularly limited as long as the pressure is the same, but the labor of exhaust can be saved and the generation of stress on the film 10 due to the occurrence of differential pressure with the outside can be prevented. It is preferable to use atmospheric pressure.
  • the adsorption / desorption substrate 30 is cooled to adsorb the evaluation target component on the substrate.
  • This adsorption may be by diffusion.
  • the gas containing the component to be evaluated is circulated and brought into contact with the base material 30, whereby the adsorption can be performed more efficiently.
  • a small amount of plasticizer and oil released from the membrane 10 are also adsorbed and fixed, but can be detected separately as described later.
  • the time for which the evaluation target component is adsorbed on the base material 30 varies depending on the amount of the evaluation target component that has permeated through the membrane 10 and the nature of the base material 30, but may normally be about 10-30 minutes.
  • the cooling of the base material 30 is stopped or heated to raise the temperature of the base material, and the evaluation target component adsorbed on the base material is desorbed.
  • the temperature of the substrate 30 is preferably increased so that the gas release rate is 1 ⁇ 10 ⁇ 9 Pa ⁇ m 3 / m 2 s or less. Further, the temperature rise is preferably performed so that the total amount of the component to be evaluated adsorbed on the substrate 30 is desorbed in 5 to 60 minutes, and more preferably desorbed in 5 to 30 minutes.
  • the analysis step needs to be performed after the substrate 30 or the tank 51 is evacuated, but when using an analysis means that does not require evacuation, The desorbed evaluation target component may be moved to the analysis means together with the inert gas.
  • the analysis of the component to be evaluated desorbed from the base material 30 is preferably performed simultaneously with the temperature rise of the base material 30. Assuming that the time of the sampling step for bringing the component to be evaluated into contact with the membrane 10 and permeating the membrane is X, and the time for raising the temperature to desorb the total amount of the component to be evaluated adsorbed on the substrate 30 is Y.
  • the evaluation target component having a concentration X / Y times that of the conventional method of analyzing the evaluation target component while evacuating is used for detection. For example, when the sampling process X is 10 hours and the temperature rising time Y is 15 minutes, the evaluation target component having a concentration 40 times that of the conventional method is provided for the analysis process.
  • the evaluation target component is not uniformly desorbed in the temperature rising process of the substrate 30, but desorbs with a specific peak (holding time) as in the chromatographic analysis (see FIG. 2). For this reason, a highly sensitive measurement with a large S / N ratio can be performed. Further, it is possible to distinguish and detect a trace amount of plasticizer or oil released from the film 10 based on the difference in holding time and the component to be evaluated. For this reason, due to the synergistic effect of the concentration of the evaluation target component and the improvement of the S / N ratio, the measurement method of the present invention can perform the permeability evaluation with remarkably superior sensitivity compared to the conventional method.
  • the evaluation target component is water vapor
  • the measurement sensitivity of the water vapor transmission amount can be increased to about 10 ⁇ 6 g / m 2 / day.
  • the analysis is preferably performed using any one of a mass spectrometer, a gas chromatography, and a vacuum gauge.
  • a mass spectrometer e.g., a mass spectrometer
  • a gas chromatography e.g., a vacuum gauge
  • a vacuum gauge e.g., a vacuum gauge
  • water, oxygen, a carbon dioxide, nitrogen, ethylene gas, or a volatile organic compound e.g., water, oxygen, a carbon dioxide, nitrogen, ethylene gas, or a volatile organic compound can be mentioned.
  • an inert gas that has been dried and removed in advance before the sampling step.
  • the inside of the chamber 15 is hermetically sealed and the inside of the chamber 15 is always evacuated or a gas not containing the evaluation target component is allowed to flow and circulate in the chamber 15. Even when there is an airtight leak between 10 and the tank 11 or between the film 10 and the tank 12, the influence on the measurement result can be suppressed to a minimum.
  • the adsorption fixing step by closing the valve and disconnecting the gas between the base material 30 and the membrane 10, it avoids the occurrence of a differential pressure on both sides of the membrane 10 due to the cooling of the gas, and damages the membrane 10. Can be prevented. Specifically, it is preferable to disconnect communication between the tanks 12 and 13 close to the membrane 10.
  • Examples of the film to be measured 10 to be evaluated for permeability in the present invention include plastic films for packaging such as foods, pharmaceuticals, and precision instruments, and barrier films for various device elements.
  • Examples of the material for the plastic film include PET (polyethylene terephthalic acid), PC (polycarbonate), PES (polyether sulfone), and COP (cycloolefin polymer).
  • An example of the area of the film to be measured 10 through which the evaluation target component permeates can be 10 cm 2 .
  • the film to be measured 10 since the film to be measured 10 is sandwiched by the support jig 14, the film to be measured 10 having various thicknesses can be accommodated, and the film thickness is not particularly limited. it can.
  • the apparatus and method of the present invention will be described with reference to FIG. 1, taking as an example the case where the component to be evaluated is water vapor.
  • water vapor that is a component to be evaluated is supplied to the tank 11.
  • the water vapor is supplied from the evaluation target component storage tank 40 to the tank 11 through the pipe 41 having a valve and is circulated through the exhaust port 62, and the inside of the tank 11 is filled with water vapor saturated or at a predetermined partial pressure.
  • the opening of the tank 12 is in contact with the opening of the tank 11, and a support jig 14 for the film 10 is provided at these contact parts, and the film 10 is formed by the support jig 14. Supported in an airtight state.
  • a tank 12 is provided opposite to the tank 11 through the membrane 10, and the inside of the tank 12 is replaced with a high-purity inert gas supplied from an inert gas tank 87, and the same pressure as the tank 11 (for example, 1 atm). Further, the high purity inert gas is also supplied into the chamber 15 in which the tanks 11 and 12 are housed, so that the water vapor in the tank 11 does not enter the tanks 11 and 12 and the like from portions other than the film 10. ing.
  • a high-purity inert gas supplied from an inert gas tank 87, and the same pressure as the tank 11 (for example, 1 atm). Further, the high purity inert gas is also supplied into the chamber 15 in which the tanks 11 and 12 are housed, so that the water vapor in the tank 11 does not enter the tanks 11 and 12 and the like from portions other than the film 10. ing.
  • a predetermined time for example, 1 to 12 hours
  • the valves of the pipes 20 and 22 are opened, the forced circulation fan 21 is operated, and the water vapor accumulated in the tank 12 is guided into the tank 13.
  • the pipes 20 and 22 are opened, and the gas in the tank 12 and the tank 13 is forcedly circulated using a fan or diaphragm pump capable of being heated and baked, and the gas is allowed to pass for a predetermined time (eg, 1 to 12 hours) Water vapor may be accumulated in the tank 12 and the tank 13.
  • the valves of the pipes 20 and 22 are closed, and the gas exchange between the tank 12 and the tank 13 is cut off while keeping the film to be measured 10 at atmospheric pressure.
  • the water vapor in the tank 13 is sent by diffusion to a water vapor capturing tank 51 equipped with a cooling means 52 (for example, a liquid nitrogen container), and is provided in the tank 51 by waiting for a predetermined time (for example, 10 to 30 minutes).
  • a predetermined time for example, 10 to 30 minutes.
  • Water vapor is adsorbed and fixed by the water vapor adsorption / desorption substrate 30.
  • organic components such as a small amount of plasticizer and oil released from the film 10 are also adsorbed and fixed.
  • the inside of the tank 51 is evacuated (for example, 10 ⁇ 5 Pa) by the ultra-high vacuum exhaust device 73 via the pipe 71 having a valve, thereby removing the inert gas existing in the tank 51. .
  • the water adsorbed on the adsorption / desorption substrate 30 is vaporized by stopping cooling with liquid nitrogen or heating the tank 51 at a constant temperature with a heater (not shown).
  • the water vapor partial pressure of the vaporized water vapor is detected by the mass spectrometer 72, and the detection result is analyzed by the computer 90. Based on the analysis result, the water vapor permeability of the membrane 10 is calculated and evaluated.
  • Example 1 The permeability evaluation method of the present invention will be specifically described with reference to FIG. 1 showing the apparatus of the present invention.
  • a test piece (provided by Oike Kogyo Co., Ltd.) whose water vapor permeability is measured to be 5.3 ⁇ 10 ⁇ 3 g / m 2 / day in an existing apparatus is used. Used as.
  • a test piece as the film to be measured 10 was sandwiched and fixed between the contact portions of the tank 11 and the tank 12 of the permeability evaluation apparatus of the present invention.
  • the area of the surface where the test piece comes into contact with the gas in the tank 11 is about 10 cm 2 .
  • a supporting jig 14 made of Viton (registered trademark), which is an elastomer, is provided at a contact portion between the tank 11 and the tank 12, and this is in close contact with and supports the test piece. Subsequently, the inside of the tank 12, the tank 13, and the chamber 15 was replaced with an inert gas.
  • the tank 11 was filled with saturated water vapor (1 atm), the inside of the tank 12 was maintained at 1 atm, and left for 15 hours while circulating with the tank 13.
  • the valves 20 and 22 were closed to prevent gas movement with the tank 12, and then the water vapor in the tank 13 was adsorbed to the adsorption / desorption substrate 30 in the tank 51 for 30 minutes.
  • the tank 51 is installed in a liquid nitrogen container as the cooling means 52 and is cooled to the liquid nitrogen temperature.
  • the porous stainless steel material for air filters made from Swagelok was used as the base material 30, the porous stainless steel material for air filters made from Swagelok was used.
  • the valve of the pipe 50 was closed, the valve of the pipe 71 was opened, and the inert gas was exhausted by the ultra-high vacuum exhaust device 73 for 20 minutes.
  • the liquid nitrogen was removed from the liquid nitrogen container 52, and the water vapor partial pressure was detected by the mass spectrometer as the analyzing means 72 while raising the temperature of the base material 30, and the detection result was analyzed by the computer 90. It was confirmed by the measurement of a thermocouple thermometer attached to the tank 51 that the temperature of the tank 51 increased at a constant temperature increase rate (12 ° C./min) from ⁇ 169 ° C. to ⁇ 100 ° C.
  • FIG. 2 shows the result of plotting the output (ion current, unit: pA) of the mass 18 amu (corresponding to H 2 O) of the mass spectrometer (Anelva QIG-066) against time.
  • FIG. 2 shows that a signal indicating a clear water peak is obtained. The reason why the peak shape is different from the theoretical shape is considered to be due to uneven temperature during heating in the tank 51 having a stainless outer wall, but it can be improved by using copper having excellent heat conduction. .
  • the peak intensity is sufficiently large with respect to the background, and the transmission time of 15 hours used in this example is considered to be too much for the film to be measured used in this example.
  • the background variation is less than 8 ⁇ 10 ⁇ 13 A, and the intensity of the peak minus the background is 2 ⁇ 10 ⁇ 11 A or more. Therefore, the signal of about 1/250 of this example, that is, 2 ⁇ It can be seen that the sensitivity of 10 ⁇ 5 g / m 2 / day can be measured with this apparatus in 15 hours.
  • the background signal decreases with the passage of time because of the effect that the water vapor adsorbed on the container is exhausted by the pump.
  • the vacuum piping used in this example is made of stainless steel. By using a material with less water vapor adsorption than stainless steel, it is easy to lower the background to 1/100.
  • Example 2 In this example, as the film to be measured 10, a barrier film having a configuration described in Japanese Patent Application Laid-Open No. 2007-134099 formed on a polyester film was used as a test piece.
  • FIG. 3 shows the configuration of the test piece used in the test.
  • the test piece 1 is formed by alternately forming seven layers of polyurea and alumina
  • the test piece 2 is formed by forming eleven layers of polyurea and alumina alternately.
  • the test piece 1 was used as the film 10 to be measured, and the water 10 was exposed to the water vapor in the tank 51 and the time for permeation was reduced from 15 hours to 3 hours. Adsorbed to the tank 51. Thereafter, the liquid nitrogen is removed from the liquid nitrogen container 52, and the water vapor partial pressure is detected by the mass spectrometer 72 while the temperature of the tank 51 is increased at a constant rate (10 ° C./min), and the detection result is analyzed by the computer 90. did. As a result, the water vapor permeability of the test piece 1 was 5.6 ⁇ 10 ⁇ 3 g / m 2 / day.
  • Example 3 When the measurement was performed in the same manner as in Example 2 except that the test piece 2 was used as the film to be measured 10, the water vapor permeability was 5 ⁇ 10 ⁇ 6 g / m 2 / day.
  • the measurements of Examples 2 and 3 were highly sensitive and reproducible. The measurement time could be performed within about 3 hours. On the other hand, the conventional measurement required several days of measurement.
  • the water vapor permeability of the test piece 1 was measured using a known permeability evaluation apparatus having the configuration shown in FIG.
  • the permeated component introduction tank 11 is a high-temperature and high-humidity tank, and the film to be measured 10 is installed at the boundary with the vacuum tank 92.
  • the tank 92 was evacuated and the water vapor partial pressure in the tank was measured to be 3.39 ⁇ 10 ⁇ 6 Pa.
  • dry nitrogen was humidified by the humidifying means 93 and introduced into the tank 11, thereby introducing water vapor into the tank 11.
  • the water vapor partial pressure in the vacuum chamber 92 after 80 minutes from the introduction of water vapor was 3.51 ⁇ 10 ⁇ 6 Pa.
  • the water vapor transmission rate is calculated from the pressure change shown in FIG. 4, it is 5.7 ⁇ 10 ⁇ 3 g / m 2 / day as shown in FIG.
  • the display of the partial pressure gauge has two digits after the decimal point.
  • the measurement limit is obtained from the change in partial pressure, it becomes 5 ⁇ 10 ⁇ 4 g / m 2 / day, which is consistent with the measurement limit of a commercially available water vapor permeability meter. In this example, the measurement accuracy was poor and the error was large.
  • water vapor permeability and oxygen permeability of various membranes can be measured with high accuracy and efficiency.

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Abstract

L'invention concerne un dispositif d'évaluation de la perméabilité qui évalue les agents pénétrants d'un film testé (10). Ledit dispositif comprend: une chambre (15) qui comporte un récipient (11) d'introduction d'agent pénétrant et un récipient (12) de passage d'agent pénétrant; un substrat (30) d'adsorption/désorption; des moyens d'analyse (72) pour analyser l'agent pénétrant évalué; et un mécanisme (80) qui alimente en gaz inerte au moins le récipient (12) de passage d'agent pénétrant. Des éléments de fixation (14) servant à maintenir le film (10) sont placés dans les deux récipients (11, 12) de la chambre (15). Quand le film (10) est maintenu par les éléments de fixation (14), un espace hermétique est formé entre une surface du film (10) et la paroi intérieure d'un récipient (11), ainsi qu'entre l'autre surface du film (10) et la paroi intérieure de l'autre récipient (12). Le récipient (11) d'introduction d'agent pénétrant comporte un orifice d'entrée (60) pour l'agent pénétrant évalué, et un orifice de sortie (62). Le récipient (12) de passage d'agent pénétrant fournit au substrat (30) l'agent pénétrant ayant traversé le film (10). Des moyens (72) permettent de détecter l'agent pénétrant désorbé par le substrat (30).
PCT/JP2010/056295 2009-04-07 2010-04-07 Dispositif d'évaluation de la perméabilité et procédé d'évaluation WO2010117012A1 (fr)

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JP2012154838A (ja) * 2011-01-27 2012-08-16 Technoeye Inc 水蒸気透過率測定装置および測定方法
JP2013003028A (ja) * 2011-06-20 2013-01-07 Sumika Chemical Analysis Service Ltd 測定装置および測定方法
US20140352413A1 (en) * 2013-06-04 2014-12-04 Samsung Electro-Mechanics Co., Ltd. Moisture transmission testing instrument
JP2015190884A (ja) * 2014-03-28 2015-11-02 三菱電機株式会社 ガス透過度測定装置
CN105510142A (zh) * 2016-01-15 2016-04-20 太原理工大学 一种煤岩多相不同流体三轴压裂试验装置与试验方法
CN108007843A (zh) * 2017-12-19 2018-05-08 中国石油天然气集团公司 一种用于评价高温高压下溶解氧在防腐涂层中渗透性的装置及方法
CN108344674A (zh) * 2017-01-25 2018-07-31 济南思克测试技术有限公司 一种基于人工智能的气体透过率自动测试系统及方法
US11119023B2 (en) * 2017-02-27 2021-09-14 National Institute Of Advanced Industrial Science And Technology Apparatus for evaluating gas barrier properties and method of evaluating gas barrier properties
WO2022189296A1 (fr) * 2021-03-12 2022-09-15 Robert Bosch Gmbh Appareil de mesure pour détermination de perméabilité aux gaz par échantillonneur, et son procédé de fonctionnement
CN117368071A (zh) * 2023-12-06 2024-01-09 德州中瑞土工材料工程有限公司 一种土工膜渗透性能测试设备
JP7590025B2 (ja) 2023-03-16 2024-11-26 江蘇科技大学 多孔質媒体の流量特性パラメータの測定装置および方法

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KR101764878B1 (ko) * 2016-03-31 2017-08-03 성균관대학교산학협력단 포화 전해질 용액을 이용한 수분 투과도의 측정 장치 및 측정 방법
CN107490539A (zh) * 2017-08-23 2017-12-19 成都本华清博科技有限公司 一种片状材料透湿性的测量装置及其测量方法
CN113495047B (zh) * 2020-04-03 2022-06-24 氢源科技(赣州)有限公司 一种燃料电池气体扩散层的性能测试装置及方法

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Publication number Priority date Publication date Assignee Title
JP2012154838A (ja) * 2011-01-27 2012-08-16 Technoeye Inc 水蒸気透過率測定装置および測定方法
JP2013003028A (ja) * 2011-06-20 2013-01-07 Sumika Chemical Analysis Service Ltd 測定装置および測定方法
US20140352413A1 (en) * 2013-06-04 2014-12-04 Samsung Electro-Mechanics Co., Ltd. Moisture transmission testing instrument
JP2015190884A (ja) * 2014-03-28 2015-11-02 三菱電機株式会社 ガス透過度測定装置
CN105510142A (zh) * 2016-01-15 2016-04-20 太原理工大学 一种煤岩多相不同流体三轴压裂试验装置与试验方法
CN108344674A (zh) * 2017-01-25 2018-07-31 济南思克测试技术有限公司 一种基于人工智能的气体透过率自动测试系统及方法
CN108344674B (zh) * 2017-01-25 2023-12-26 济南思克测试技术有限公司 一种基于人工智能的气体透过率自动测试系统及方法
US11119023B2 (en) * 2017-02-27 2021-09-14 National Institute Of Advanced Industrial Science And Technology Apparatus for evaluating gas barrier properties and method of evaluating gas barrier properties
CN108007843A (zh) * 2017-12-19 2018-05-08 中国石油天然气集团公司 一种用于评价高温高压下溶解氧在防腐涂层中渗透性的装置及方法
CN108007843B (zh) * 2017-12-19 2024-01-30 中国石油天然气集团公司 一种用于评价高温高压下溶解氧在防腐涂层中渗透性的装置及方法
WO2022189296A1 (fr) * 2021-03-12 2022-09-15 Robert Bosch Gmbh Appareil de mesure pour détermination de perméabilité aux gaz par échantillonneur, et son procédé de fonctionnement
JP7590025B2 (ja) 2023-03-16 2024-11-26 江蘇科技大学 多孔質媒体の流量特性パラメータの測定装置および方法
CN117368071A (zh) * 2023-12-06 2024-01-09 德州中瑞土工材料工程有限公司 一种土工膜渗透性能测试设备
CN117368071B (zh) * 2023-12-06 2024-02-09 德州中瑞土工材料工程有限公司 一种土工膜渗透性能测试设备

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